Ion Size Research Articles

BaSn0.96-XZr0.04MXO3 (M = Mn, Fe or Co, x = 0, 0.02) for spin-based devices: Ferromagnetic properties

In this study, Zr and/or Mn, Fe or Co ions were used to induce a robust room temperature ferromagnetic nature in perovskite BaSnO3 for high performance information applications. Dilute magnetic semiconductor compositions with formula of BaSn0.96-XZr0.04MXO3 (M = Mn, Fe, Co, x = 0, 0.02) have been synthesized at 1150 °C. For all compositions, mono-phase of cubic BaSnO3 structure with very small impurities of SnO2 were recorded based on X-ray diffraction analysis. The relation between ionic size of dopants and crystal dimension of BaSnO3 suggests the of Sn4+-site by Zr4+, Mn2+, Fe2+ or Co2+ ions. Extended absorption tails to visible light region were found for BaSn0.94Zr0.04Mn0.02O3 and BaSn0.94Zr0.04Co0.02O3 samples, owing to strong defect band transition absorption. Due to the addition of Zr and/or Mn, Fe or Co ions high refine of BaSnO3 morphology from inhomogeneous large grains to well distribute small one were seen. The XPS results of BaSn0.96Zr0.04O3 and BaSn0.94Zr0.04Co0.02O3 samples confirm that Ba, Sn, O and Zr are in the oxidation states of +II, +IV, −II and +IV/+III, respectively. Magnetically, incorporation of 4 wt% Zr4+ ions (empty 4d-orbital) induced a full-saturated spin ferromagnetic order with saturation magnetization of 1.16 emu/g, retentivity of 0.11 emu/g and coercivity of 147 Oe. Also, codoping by Zr/Co ions stimulates a full-saturated spin ferromagnetic order with saturation magnetization of 1.36 emu/g, retentivity of 0.17 emu/g and coercivity of 149 Oe. The empty 4d-Zr4+ ions have high ability in reversing the diamagnetic nature of BaSnO3 to ferromagnetic one through interaction with oxygen vacancies. The outer 4d-shell of Zr and 3d-orbital of Co with the oxygen vacancies induce the strong magnetic exchange interaction. Through looking into the previous studies on the magnetic properties of BaSnO3, the recorded saturation magnetization of 4 wt% Zr and 4 wt% Zr + 2 wt% Co ions are remarkable values.

Ion Steric Effect Induces Giant Enhancement of Thermoelectric Conversion in Electrolyte-Filled Nanochannels.

Ionic thermoelectricity in nanochannels has received increasing attention because of its advantages, such as high Seebeck coefficient and low cost. However, most studies have focused on dilute simple electrolytes that neglect the effects of finite ion sizes and short-range electrostatic correlation. Here, we reveal a new thermoelectric mechanism arising from the coupling of the ion steric effect due to finite ion sizes and ion thermodiffusion in electric double layers, using both theoretical and numerical methods. We show that this mechanism can significantly enhance the thermoelectric response in nanoconfined electrolytes depending on the properties of electrolytes and nanochannels. Compared to the previously known mechanisms, the new mechanism can increase the Seebeck coefficient by 100% or even 1 order of magnitude enhancement under optimal conditions. Moreover, we demonstrate that the short-range electrostatic correlation can help preserve the Seebeck coefficient enhancement in a weaker confinement or in more concentrated electrolytes.

Effect of Ion Size on Pressure-Induced Infiltration of a Zeolite-Based Nanofluidic System.

A nanofluidic system consists of a nano-porous medium and functional liquid, which demonstrates a higher energy absorption density compared to conventional systems for energy absorption. Alterations in the composition of the functional liquid can significantly impact the properties of a nanofluidic system. In this paper, the widely used zeolite ZSM-5 was chosen as the porous medium to establish a nanofluidic system. Three distinct electrolyte solutions, namely KCl aqueous solutions, NaCl aqueous solutions and MgCl2 aqueous solutions were employed as functional liquids while pure water served as the reference condition for configuring four kinds of nanofluidic systems. Pressure-induced percolation experiments were performed on the four zeolite-based systems. The difference in the infiltration process between the electrolyte solution systems and the deionized water system has been ascertained. The effect of the ion size on the infiltration and defiltration process has been determined. The results show that the introduction of ions induces a hydration effect, resulting in a higher critical infiltration pressure of the electrolyte solution system compared to an aqueous solution system. The magnitude of cation charge directly correlates with the strength of the hydration effect and the corresponding increase in critical infiltration pressure. Upon entering the nanochannel, the liquid infiltrates primarily in the form of ions rather than a cation hydration form. The larger the ion size, the shallower the penetration depth after entering the nanopore channel and the larger the corresponding relative outflow rate. The present work will provide valuable theoretical complementary and experimental data support for nanofluidic system applications.

Structure, spectroscopy, and metal exchange among M(III) clusters with salicylidene-α-hydroxy acid chelates (M = Al, Ga, In, Fe)

The tetradentate salicylidene-α-hydroxy acid chelate, 3,5-diCl-Sal-AHA, was previously shown to form trinuclear clusters with the similarly-sized Fe(III) and Ga(III) ions, but a binuclear structure was observed with the much larger uranyl ion. To determine the structural effect of ionic size, complexes of 3,5-diCl-Sal-AHA with the smaller Al(III) ion and larger In(III) ion were prepared. X-ray data show that Al(III) forms a trinuclear cluster similar to those of Fe(III) and Ga(III). However, ESI-MS data show that Al(III) trinuclear clusters exist in equilibrium with binuclear clusters, with basic conditions favoring increased binuclear cluster formation. X-ray data from a crystal obtained from basic solution of Al(III) with 3,5-diCl-Sal-AHA show a binuclear, carbonato-bridged complex. ESI-MS data for the In(III) complex indicate that it forms a trinuclear cluster. The Fe(III), Ga(III), Al(III), and In(III) complexes all have strong circular dichroism spectra, while only the Al(III), Ga(III), and In(III) complexes are fluorescent. When the Group 13 metal complexes are treated with ferric chloride, Fe(III) displaces Al(III), Ga(III), and In(III) in aqueous methanol, but no metal exchange occurs in dry methanol.

Unexpectedly Enhanced Organics Removal in Persulfate Oxidation with High Concentration of Sulfate: The Origin and the Selectivity.

Massive anions in high saline wastewater are primary factors that restricted the efficiency of pollutant degradation in advanced oxidation processes (AOPs). Herein, we reported the influence laws of different anions at high concentration on the electron-transfer process in the activation of persulfate, and especially, the sulfate anion exhibited the excellent promotion effect. Depending on the ionic charge, polarizability, and size, the anions exerted diverse effects on the dispersed phase and zeta potential of carbonaceous catalysts, which further embodied in the removal of pollutants. Based on the differences of reaction rate constant in water solution and high saline solution, the order was ClO4- < NO3- < Cl- < SO42- < CO32-, obeying the Hofmeister series. The enhancement of the sulfate anion was widely confirmed with different carbonaceous catalysts and pollutants with various structures. It could be attributed to the higher oxidation capacity, the faster interfacial electron transfer, and the better catalyst dispersion in the high sulfate environment. On the other hand, the decrease of zeta potential of the catalyst induced by sulfate reinforced the electrostatic attraction or repulsion with pollutants, which caused the selectivity of the sulfate promotion effect. Overall, this study provides new insights into the mechanism of influence of anions on AOPs, which refreshed the cognition of the role of sulfate on pollutant degradation, and helps guide the treatment design of high salinity wastewater.

To a Question of Sulfur Sites in Crystal Structures of Tetrahedrite Group Minerals: Relationships between Occupancy, Effective Ion Sizes, and Unit Cell Parameters

To a Question of Sulfur Sites in Crystal Structures of Tetrahedrite Group Minerals: Relationships between Occupancy, Effective Ion Sizes, and Unit Cell Parameters

Effects of lattice distortion and amount of d electrons on the pressure-driven structural phase transition in ZnO: A comparative study of V-, Mn-, and Co-doped ZnO

The pressure-driven phase transition from fourfold würtzite (B4) to sixfold coordinated rock salt (B1) structure in ZnO, in particular in transition metal (TM) doped ones, exhibited very scattered results and remained as an outstanding issue. The in situ angle-dispersive x-ray diffraction revealed that TM doping can result in significant reduction on the onset pressure at which the pressure-driven B4-to-B1 phase transition starts to emerge, albeit the transition path appeared to be very much dependent on the doping transition metal element. Systematic comparisons on a series of V-, Mn-, and Co-doped ZnO materials indicated that, in addition to ionic sized difference-induced lattice distortion, the amount of the 3d electrons carried by the doped TM atom may also play a prominent role in the underlying mechanism of the pressure-driven phase transition. Specifically, the existence of 3d electrons may have resulted in increased screening of the Coulomb forces between the cations at increasing pressure, leading to significant softening of the c44 and c66 elastic constants, which, in turn, lowers the onset pressure in triggering the B4-to-B1 phase transition in ZnO. Our results also indicate that the initial lattice distortion induced by the ionic size difference may change the landscape of energy barrier and alter the phase transition path.

Impact of hierarchical water dipole orderings on the dynamics of aqueous salt solutions

Ions exhibit highly ion-specific complex behaviours when solvated in water, which remains a mystery despite the fundamental importance of ion solvation in nature, science, and technology. Here we explain these ion-specific properties by the ion-induced hierarchical dipolar, translational, and bond-orientational orderings of ion hydration shell under the competition between ion-water electrostatic interactions and inter-water hydrogen bonding. We first characterise this competition by a new length λHB(q), explaining the ion-specific effects on solution dynamics. Then, by continuously tuning ion size and charge, we find that the bond-orientational order of the ion hydration shell highly develops for specific ion size and charge combinations. This ordering drastically stabilises the hydration shell; its degree changes the water residence time around ions by 11 orders of magnitude for main-group ions. These findings are fundamental to ionic processes in aqueous solutions, providing a physical principle for electrolyte design and application.

Dual facet passivation of silver halometallate for eco-friendly silver bismuth sulfide near IR photodetector

Ternary chalcogenide silver bismuth sulfide nanocrystals (AgBiS2 NCs) have taken great strides in the past few years to emerge as one of the better eco-friendly alternatives to compete with the prevalent toxic semiconductor materials such as lead sulfide quantum dots (PbS QDs) in the near-infrared (NIR) region. Nevertheless, their implementation in photodetectors has been scarce due to high dark current and complicated solid-state ligand exchange fabrication steps involved, resulting in a lower overall detectivity. The performance is further deemed to be stunted due to the difficulty associated with the passivation of the charge-neutral (100) facet of larger AgBiS2 NCs efficiently. In this work, we aimed to develop a mixed ‘halometallate’ ligand approach, wherein we introduce silver bromide (AgBr) as an ancillary ligand to silver iodide (AgI), passivating both (100) and (111) facets of cubic AgBiS2 solids in a facile solution-phase ligand exchange step to obtain highly dispersible colloidal ink. Decreased bond length, bond angle (Br-Ag-Br), and ionic size of [AgBr2-] anion induces less compressive strain compared to [AgI2–], culminating in higher molecular stability on the AgBiS2 surface. This dual passivation reduces the dark current to 6.01 × 10-7 A cm−2 and a high specific detectivity of 1.8 × 1012 Jones at 800 nm is achieved, comparable to ubiquitous PbS QD devices. We also demonstrate diminished in-gap carrier density population, enhanced light detection, and ultrafast microsecond response at higher wavelengths operating under high bias (-1V) photoconductive mode. This study illustrates the role of optimum surface coverage in eliminating the deleterious non-radiative recombination defect centers by introducing additional ligands in solution-processed AgBiS2 NC and the viability of the mixed ligand approach for stable eco-friendly NIR photodetectors.

WITHDRAWN: Crystal structure and interconversion of monomers and domain-swapped dimers of the walnut tree phytocystatin

Biotechnological applications of phytocystatins have garnered significant interest due to their potential applications in crop protection and improve crop resistance to abiotic stress factors. Cof1 and Wal1 are phytocystatins derived from Coffea arabica and Juglans regia, respectively. These plants hold significant economic value due to coffee's global demand and the walnut tree's production of valuable timber and widely consumed walnuts with culinary and nutritional benefits. The study involved the heterologous expression in E. coli Lemo 21(DE3), purification by immobilized metal ion affinity and size exclusion chromatography, and biophysical characterization of both phytocystatins, focusing on isolating and interconverting their monomers and dimers. The crystal structure of the domain-swapped dimer of Wal1 was determined revealing two domain-swapped dimers in the asymmetric unit, an arrangement reminiscent of the human cystatin C structure. Alphafold models of monomers and Alphafold-Multimer models of domain-swapped dimers of Cof1 and Wal1 were analyzed in the context of the crystal structure. The methodology and data presented here contribute to a deeper understanding of the oligomerization mechanisms of phytocystatins and their potential biotechnological applications in agriculture.

Deciphering the role of fucoidan from brown macroalgae in inhibiting SARS-CoV-2 by targeting its main protease and receptor binding domain: Invitro and insilico approach

The current study investigated the role of fucoidan from Padina tetrastromatica and Turbinaria conoides against 3-chymotrypsin like protease (3CLpro) and receptor binding domain (RBD) spike protein of SARS-CoV-2 using an invitro and computational approach. The 3CLpro and RBD genes were successfully cloned in pET28a vector, expressed in BL-21DE3 E. coli rosetta cells and purified by ion exchange affinity and size exclusion chromatography. Fucoidan extracted from both biomass using green approach, subcritical water, was found to inhibit 3CLpro of SARS-CoV-2 with an IC50 value of up to 0.35 mg mL−1. However, fucoidan was found to be inactive against the RBD protein. Molecular docking studies demonstrated that fucoidan binds to the active sites of 3CLpro with an affinity of −5.0 kcal mol−1. In addition, molecular dynamic simulations recorded stabilized interactions of protein-ligand complexes in terms of root mean square deviation, root mean square fluctuation, the radius of gyration, solvent accessible surface area and hydrogen bond interaction. The binding energy of fucoidan with 3CLpro was determined to be −101.821 ± 12.966 kJ mol−1 using Molecular Mechanic/Poisson-Bolt-Boltzmann Surface Area analysis. Fucoidan satisfies the Absorption, Distribution, Metabolism, and Excretion (ADME) properties, including Lipinski's rule of five, which play an essential role in drug design. According to the toxicity parameters, fucoidan does not exhibit skin sensitivity, hepatotoxicity, or AMES toxicity. Therefore, this work reveals that fucoidan from brown macroalgae could act as possible inhibitors in regulating the function of the 3CLpro protein, hence inhibiting viral replication and being effective against COVID-19.

Conditional existence of Donnan potential in soft particles and surfaces: Dependence on steric effects mediated by electrolyte ions and structural charges

When a charged layer decorating a particle or a macroscopic surface is equilibrated with an electrolyte solution, a constant Donnan potential is established through that layer due to charge-driven accumulation of counterions and companion exclusion of coions. This situation arises when the thickness of the surface layer well exceeds the screening Debye length, a condition derived from mean-field Poisson-Boltzmann theory within point-like charge approximation. Herein, we revisit this condition underlying the applicability of Donnan electrostatic representation with the account of steric effects mediated by the sizes of the electrolyte ions and structural layer charges. A transcendental equation is derived for the Donnan potential as a function of sizes and valences of anions and cations, electrolyte concentration and size of the layer charges, and a closed-form expression is provided for symmetrical electrolytes. Therefrom we evidence that the existence of a Donnan potential is conditioned not only to large values of the layer thickness compared to a here-defined Debye length operative within the shell, but to additional verification of a criterion that involves space charge density of the layer, solution ionic strength and electrolyte nondiluteness parameter. Illustrative computational examples show how the existence and magnitude of the Donnan potential depend on the key molecular descriptors of the electrolyte and soft interface, and they further quantify the deviations from predictions based on classical Donnan potential expression valid for dilute electrolytes.

Beam optimization of a heavy ion microbeam for targeted irradiation of mitochondria in human cells

Mitochondria, organelles of the cytoplasm, are the power plants of the cell and thus their function is important for the survival of cells. Mitochondria are known to depolarize after targeted irradiation, but the effects on cells are still unclear. The aim of this work is to investigate the effects of mitochondrial depolarization on growth and survival of cells. We performed targeted irradiation with 55 MeV C5+-ions at the ion-microbeam SNAKE at the 14 MV tandem accelerator in Garching near Munich, with a beam spot size of ∼1 µm. Approx. 6% of the mitochondrial area was irradiated in 74 cells with 5,120 carbon ions homogenously distributed over a square area of 13.2 µm2. Cell growth was investigated by observing the cells for 3.5 days via live-cell phase-contrast microscopy and evaluating the number of vital cells. While the number of irradiated cells remained constant during the observation, the unirradiated control group showed exponential growth. An additional particle track detector test with polycarbonate revealed that 4% parasitic ions hit the cells up to 500 µm away from the target, forming a so-called halo and inducing a mean parasitic dose of (2 ± 2) Gy on the cells. This dose alone, when applied in cell nuclei, is large enough to reduce the survival and growth of cells significantly and overrides any effects caused by targeted irradiation of mitochondria. Subsequently, several methods to reduce the halo were investigated. A significant reduction in halo size and number of ions in the halo could be achieved by using C6+-ions instead of C5+-ions. The slit openings, correction of lens errors, and the beam spot size had minor influence on the halo size but could achieve a reduction in halo dose. Overall, a 97% reduction in halo area and a halving of halo dose were achieved.

Scalable and highly selective graphene-based ion-exchange membranes with tunable permselectivity

Graphene oxide (GO) membranes have been proved to be ion-selective thanks to their oxidized functional groups, which are naturally present on its surface. This ion selectivity, together with good mechanical strength, low cost, and simple synthesis, makes GO a great alternative material to conventional costly polymers for the production of ion-exchange membranes. This work focuses on how to produce GO membranes as ion-exchange membranes with a scalable approach and tunable permselectivity. Their physicochemical properties were subsequently investigated by means of selected characterization techniques. Results showed that GO membranes present good ion selectivity and size exclusion towards monovalent cations, reaching a permselectivity of up to 96%. Interestingly, UV-light irradiation of GO membranes can also be proposed as a green reduction method. GO reduction increases the permselectivity due to both a decrease in the dimension of the nanochannels and a reduction in the swelling degree of the membranes. The addition of binders was also investigated to improve the membranes’ mechanical properties. Finally, the ionic resistance of the membranes was measured by impedance spectroscopy, achieving 4.6 Ω cm2, orders of magnitude lower than the state-of-the-art graphene oxide-based membranes.

Does the Sign of Charge Affect the Surface Affinity of Simple Ions?

The role the charge sign of simple ions plays in determining their surface affinity in aqueous solutions is investigated by computer simulation methods. For this purpose, the free surface of aqueous solutions of fictitious salts is simulated at finite concentration both with nonpolarizable point-charge and polarizable Gaussian-charge potential models. The salts consist of monovalent cations and anions that are, apart from the sign of their charge, identical to each other. In particular, we consider the small Na+ and the large I- ions together with their charge-inverted counterparts. In an attempt to avoid the interference even between the behavior of cations and anions, we also simulate systems containing only one of the above ions, and determine the free energy profile of these ions across the liquid-vapor interface of water at infinite dilution by potential of mean force (PMF) calculations. The obtained results reveal that, in the case of small ions, the anion is hydrated considerably stronger than the cation due to the close approach of water H atoms, bearing a positive fractional charge. As a consequence, the surface affinity of a small anion is even smaller than that of its cationic counterpart. However, considering that small ions are effectively repelled from the water surface, the importance of this difference is negligible. Further, a change in the hydration energy trends of the two oppositely charged ions is observed with their increasing size. This change is largely attributed to the fact that, with increasing ion size, the factor of 2 in the magnitude of the fractional charge of the closely approaching water atoms (i.e., O around cations and H around anions) outweighs the closer approach of the H than the O atom in the hydration energy. Thus, for large ions, being already surface active themselves, the surface affinity of the anion is larger than that of its positively charged counterpart. Further, such a difference is seen even in the case when the sign of the surface potential favors the adsorption of cations.

Effect of Divalent Cations and Other Ions on the Tetrahydrofuran Crystal Inhibition of Quaternary Ammonium Salts-Relevance to the Efficiency of Gas Hydrate Quaternary Anti-agglomerants.

Gas hydrate anti-agglomerants (AAs) are a class of low-dosage hydrate inhibitor that are used to prevent plugging of gas hydrates in oil and condensate upstream flow lines. Industrial AAs are mostly cationic surfactants which are "hydrate-philic", i.e., they are designed to interact with and modify gas hydrate crystal growth. Tetrahydrofuran (THF) hydrate crystal growth studies have been used for many years to determine useful functional groups to incorporate into AA surfactants. In particular, quaternary ammonium and phosphonium salts with optimized alkyl groups show good THF crystal growth inhibition, which is a key property for AAs. AAs are often screened and tested in model brines containing sodium chloride despite the produced water containing various divalent cations. Recent studies have shown that AAs performed better when tested in brines containing both sodium and calcium ions rather than just sodium ions. Here, we present THF hydrate crystal growth studies on quaternary ammonium and phosphonium salts and other related molecules including guanidinium salts and amine oxides. Tests were carried out with a variety of cations including sodium, calcium, magnesium, and lithium at identical pre-determined subcooling, in order to investigate the effect of the ion size and charge density on the crystal growth inhibition. We also investigate the effect of using the more polarizable iodide ions compared to chloride ions. Our results show that crystal growth inhibition in solutions with calcium ions is somewhat greater than that with sodium ions, in agreement with past studies on the effect of AA performance with mono- and divalent cations. However, the variation does not seem to be primarily related to the charge density and polarizing ability of the cations. This study therefore provides evidence that AAs should be tested in brines containing all the ions present in the produced water and not just sodium chloride brine.

Process-Gas-Influenced Anti-Site Disorder and Its Effects on Magnetic and Electronic Properties of Half-Metallic Sr2FeMoO6 Thin Films

Anti-site disorder, arising due to the similar size of Fe and Mo ions in Sr2FeMoO6 (SFMO) double perovskites, hampers spintronic applicability by deteriorating the magnetic response of this double perovskite system. A higher degree of anti-site disorder can also completely destroy the half-metallicity of the SFMO system. To study the effects of different process gas conditions on the anti-site disorder, we have prepared a series of SFMO thin films on SrTiO3 (001) single-crystal substrate using a pulsed laser deposition (PLD) technique. The films are grown either under vacuum or under N2/O2 partial gas pressures. The vacuum-grown SFMO film shows the maximum value of saturation magnetization (MS) and Curie temperature (TC), signaling the lowest anti-site disorder in this series. In other words, there is a long-range Fe/Mo-O-Mo/Fe ferrimagnetic exchange in the vacuum-grown thin film, thereby enhancing the magnetization. Further, all the SFMO films show a semiconducting state with a systematic increase in overall resistivity with the increased anti-site disorder. The electrical conduction mechanism is defined by the variable-range hopping model at low temperatures. Raman spectra show a weak Fano peak, suggesting the presence of electron–phonon coupling in SFMO thin films. These results show the significance of the process gas in causing anti-site disorder, tuning the degree of this disorder and therefore its influence on the structural, magnetic, electrical, and vibrational properties of SFMO thin films.

Bis(phenanthrolinyl)amine manganese complexes with pseudo-trigonal prismatic geometry

Two manganese(II) complexes supported by an isoamyl-substituted bis(phenanthrolinyl)amine ligand have been prepared and characterized. Determination of the molecular structures through X-ray crystallography demonstrated that the triflate compound crystallizes as a monomeric species with an outer-sphere anion, while the chloride complex exists as a dimer containing bridging chloride ligands in the solid state. Importantly, these structures revealed a coordination environment about the metal centre that is best described as pseudo-trigonal prismatic in both cases. Computational analysis found an optimized geometry for the triflate complex in a high-spin state that is consistent with the experimental observations, while the low-spin calculation showed a significant shift toward octahedral geometry. These results and their contrast with previously reported data provide evidence for the influence of electronic structure and metal ion size on molecular geometry in this system.

Development of P3-type K0.70[Cr0.86Sb0.14]O2 cathode for high-performance K-ion batteries

Potassium-ion batteries (KIBs) are one of the most promising alternatives to lithium-ion batteries because of the high standard hydrogen electrode of K+/K, which is the second lowest after lithium. However, the large ionic size of K+ generally hinders the reversible intercalation and results in the undesirable structural changes during charge-discharge process. Thus, it is very important to develop stable cathode materials that accommodate K+ into their crystal structure with minimal structural changes. Here we propose P3-type K0.70 [Cr0.86Sb0.14]O2 as a potential cathode material for high-performance KIBs. The P3-type K0.70 [Cr0.86Sb0.14]O2 was successfully fabricated via electrochemical ion-exchange of Na+/K+. At a current density of 15 mA/g, P3–K0.70 [Cr0.86Sb0.14]O2 delivered a reversible capacity of 126.1 mAh/g with a high coulombic efficiency of 98.7%, corresponding to the de/intercalation of 0.57 mol of K+ ions from/into the structure. In addition, P3-type K0.70 [Cr0.86Sb0.14]O2 showed excellent cycling stability over 200 cycles at a current density of 150 mA/g and power capability even at high current rate of 750 mA/g. In contrast, P3-KxCrO2 demonstrates inferior electrochemical properties; this comparison implies that substitution of 0.14 mol Sb into Cr sites significantly improves structural stability with reversible Cr3+/4+ redox reaction during charge-discharge process.

Biphasic high-entropy layered oxide as a stable and high-rate cathode for sodium-ion batteries

O3-phase layered oxides are promising cathode materials for sodium-ion batteries. However due to the strong Na+–O2- electrostatic attraction and the large size of Na ion, the O3 type cathodes suffer inferior rate capability and undesired phase transitions induced fast capacity fading. Herein, we propose a synergetic strategy of secondary phase (P2) and high-entropy to alleviate the aforementioned problems. Such a novel biphasic high-entropy (B-HE) layered cathode Na0.85Li0.05Ni0.25Cu0.025Mg0.025Fe0.05Al0.05Mn0.5Ti0.05O2 exhibits a specific capacity of 122 mAh g−1 at 0.2C, outstanding rate capacity of 81.8 mAh g−1 at 10C, and long-term cycling stability of ∼ 90% capacity retention after 1000 cycles at 10C. In situ XRD and electrochemical characterization demonstrate reversible phase transition of O3/P2 ↔ P3/P2 ↔ OP2/OP4, and the long-term existed P phase with fast Na ion migration paths. This biphasic high-entropy design strategy provides a promising road for advanced cathodes of Sodium-ion batteries.